Unsaturated carbamyl or acyloxy containing phosphorothioates and phosphorodithioates



United States Patent 3,431,325 UNSATURATED CARBAMYL 0R ACYLOXYCONTAINING PHOSPHOROTHIOATES AND PHOSPHORODITHIOATES Sheldon B.Greenbaum, Tonawanda, N.Y., assignor to Hooker Chemical Corporation,Niagara Falls, N.Y., a corporation of New York No Drawing.Continuation-impart of application Ser. No. 322,526, Nov. 8, 1963. Thisapplication Feb. 28, 1966, Ser. No. 530,331

wherein R and R are .alkyl of from 1 to about 6 carbon atoms;

Q is selected from the group consisting of oxygen and sulfur;

X is selected from the group consisting of chlorine, bromine, andhydrogen;

B and B are selected from the group consisting of hydrogen and alkyl of1 to about 6 carbon atoms;

Y is selected from the group consisting of wherein:

Z and Z are selected from the group consisting of hydrogen and an alkylof 1 to about 6 carbon atoms;

Z is selected from the group consisting of alkyl of l to about 6 carbonatoms, unsubstituted aryl of from 6 to about 14 carbons atoms, andchloro-substituted aryl of 6 to about 14 carbon atoms;

Q is selected from the group consisting of oxygen and sulfur; and

R is selected from the group consisting of hydrogen,

alkyl of from 1 to 6 carbon atoms and wherein B, B and Y are asdescribed above, said X substituent being hydrogen only when Q issulfur.

The compounds of this invention are useful as pesticides.

This is a continuation-in-part of Ser. No. 322,526, filed Nov. 8, 1963,now US. Patent 3,326,943.

This invention relates to new compositions of matter and to processesfor producing them. More specifically, the present invention is fornovel organic phosphorothioates and phosphorodithioate esters containingin one of the ester groups both an unsaturated carbon-to-carbon linkageand a canbamate, carbonate, thiocarbonate, furoate, or formate grouping,and processes for the preparation thereof.

The compounds of the invention are useful as pesticides, pesticideintermediates and as organic intermediates, as will be more fullydescribed herein.

3,431 ,325 Patented Mar. 4, 1969 "ice The novel compounds of thisinvention are represented by the following formula:

RO Q X B i s-om= hoY 1 RO/ 1 wherein R and R are alkyl radicals,preferably of 1 to about 6 carbon atoms;

Q is selected from the group consisting of oxygen and sulfur;

X is a halogen atom, preferably chlorine or bromine, and

hydrogen;

B and B are selected from the group consisting of hydrogen and alkyl,preferably of 1 to 6 carbon atoms;

Y is selected from the group consisting of radicals represented by thefollowing formulas:

0 and il-QZ wherein Z and Z are selected from the group consisting ofhydrogen, and alkyl radicals, preferably of 1 to *6 carbon atoms;

Z is selected from the group consisting of alkyl, aryl, and heterocyclicradicals; and Q is selected from the group' consisting of oxygen andsulfur; and

R is selected from the group consisting of hydrogen, alkyl, preferablyof l to 6 carbon atoms and a radical of the formula:

wherein B, B and Y are as defined herein; said X substituent beinghydrogen only when Q is sulfur.

Illustrative examples of the alkyl substituents are methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, eicosyl, and the like, the alkylgroup being defined as a monovalent radical derived from an aliphatichydrocarbon by removal of one hydrogen atom, which may contain from 1 toabout 20 carbon atoms, preferably containing from 1 to about 6 carbonatoms.

When the substituent Z is alkyl, the alkyl group may be substituted bysubstituents such as alkoxy, 'i.e., methoxy, propoxy, pentoxy, etc.,halogen and vinyl, or the alkyl group may be a cyclic alkyl such ascyclohexyl, cyclooctyl, and cyclopentenyl.

When Z is an aryl substituent, it preferably contains 6 to about 14carbon atoms and includes such radicals as phenyl, naphthyl, anthryl,and the like. The aryl group may be defined as any organic radicalderived from an aromatic hydrocarbon by the removal of one hydrogenatom. The aryl radical may be substituted by substituents such as halo,alkyl, nitro, alkoxy, and like substituents.

Where Z is a heterocyclie radical, it may be an organic radicalcontaining a dissimilar atom or atoms, not carbon, in the ring,generally containing 1 to about 30 carbon atoms or more, preferablycontaining 1 to about 12 carhon atoms, such as pyranyl,tetrahydrothienyl, pyridylmethyl, furfuryl, tetrahydrofurfuryl, thienyl,furyl, and the like.

In a preferred embodiment, the heterocyclic atom is selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and the like,it being appreciated that other heterocyclic atoms such as arsenic arebeing embraced herein.

Illustrative examples of the compounds included within the presentinvention are represented by the following structures which are notintended to be limiting.

Carbamates Carbonate derivatives 4 l Thiocarbonate derivatives Thecompounds embraced within this invention thus contain a phosphorus atomlinked through a sulfur atom to a vinyl carbon atom. The carbon atom onthe other end of the vinyl group has one of its valences attached to anisolating carbon atom and the other valence is linked to a hydrogen atomwhen the phosphorus ester is a phosphorodithioate, and a halogen atom,preferably chlorine or bromine when the ester is a phosphorothioate. Theisolating carbon atom can be attached to a carbamate, carbonate,thiocarbonate, furoate or formate group. The carbon atom to which thephosphorus atom is linked through sulfur may also be attached to anisolating carbon which, in turn, is attached to another carbamate,carbonate, thiol carbonate furoate or formate group.

The novel compounds of the present invention can be prepared by severalmethods. A convenient method for the preparation of the novelphosphorodithioate compounds of the present invention comprises reactinga phosphorodithioic acid of the formula:

with an alkyne of the formula:

wherein the substituents R, R, R B, B and Y are as defined herein. Thisreaction is generally accomplished in the liquid phase at thetemperature in the range from about 25 degrees centrigrade to about 200degrees centigrade, with the preferred temperature being 25 to aboutdegrees centigrade. Other temperatures can be utilized which will notadversely affect the reaction mechanism.

If desired, a solvent may be employed to facilitate the reaction. Amongthe suitable solvents are, e.g., benzene, toluene, ether, hexane,dioxane and the like.

The compounds of the invention where Q is oxygen and X is halogen areprepared by reacting the alkyne of Formula HI above with adialkoxyoxophosphorane sulfenyl halide (also calleddialkoxyphosphinyl-sulfenyl halide) of the formula:

wherein the substituents R, R and X are as defined herein.

The reaction is generally accomplished with the temperature being in therange from about -40 degrees centigrade to about 60 degrees centigrade,the preferred temperature being about 25 to about 60 degreescentrigrade. Other temperatures which will not adversely affect thereaction mechanism can be utilized.

If desired, an inert solvent may be employed to facilitate the reaction.Among the suitable solvents are, e.g., carbon tetrachloride,trichloroethylene, tetrachloroethane, ethyl ether, tetrahydrofuran andthe like. In a like manner, irradiation, especially with ultravioletlight generally accelerates the reaction.

Generally, the reactants are reacted in molar ratios. The molar ratio ofalkyne to phosphorodithioic or dialkoxyoxophosphorane sulfenyl halide isgenerally in the vicinity of 1:1, but an excess of the alkylne is notharmful. The alkynes of Formula HI are readily prepared from materialswhich are generally commercially available. Thus propargyl alcohol,methyl butynol or 1,4- butynediol can be converted to theirchlorocarbonaltes via reaction with phosgene and those, in turn, can bereacted with alcohols, amines, mercaptans, and other nucleophiles togive the desired intermediates. Alternatively, the propargyl alcohol canbe treated with a substituted acid or acid chloride to give the desiredintermediate.

The dialkoxyoxophosphorane sulfenyl halides of Formula II I may beprepared by reacting the corresponding trialkyl thiophosphate withsulfuryl halide at low temperatures, generally below about 30 degreescentrigrade and if desired in the presence of a solvent such as carbontetrachloride, trichloroethylene, ethyl ether and like solvents.

The dialkoxyphosphorodithioic acids are readily prepared from theappropriate alcohol and P 8 in a solvent such as toluene or benzene.

The compounds of this invention possess an unusually broad spectrum ofpesticidal activity. Thus, the compositions are effective for thecontrol of a large variety of insects such as flies, mosquitoes,roaches, beetles, silverfish, mites and the like. Many of the relatedcompositions of the prior art are very specific in their insecticidalactivity so as to require the use of other insecticides. In mostinstances this makes such prior art insecticides commerciallyunsuitable. By contrast, the compositions of this invention areespecially suitable for crop and garden use where many difierent speciesof insects are encountered. A further advantage over relatedcompositions of the prior art is that the compounds of the inventionexhibit systemic properties, that is, they can translocate from one partof a plant to another, and thus give very thorough protection againstinsect attack on the plant. They are also very elfecti ve againstinternal pests such as leaf miners.

An additional advantage of these novel compounds is that they may beutilized as pesticides in various grades of purity, ranging from a crudereaction mixture up to a highly refined product. Preferably, however, aneffective amount, generally in phytotoxic concentration of the compoundof the present invention is applied to the locus to be treated for bestcontrol of undesired pests. Furthermore, these compositions may becombined with other pesticides, for example, insecticides, such as DDT,methoxychlor, lindane, aldrin, endrin, benzenehexachloride, parathion,malathion, methyl parathion, lead and other metallic arsenates,rotenone, allethrin, pyrethrum, nicotine, summer oils, dormant oils,petroleum fractions and distillates, dinitroalkylphenols,dinitrocresols, chlordane, heptachlor, chlorinated terpenes, demeton,other insecticidal organophosphates, thiophosphates and dithiophosphatessuch as those commercially designed as Guthion, Diazinon, Dibrom andothers; miticides such as bis :(pentachlorocyclopentadienyl),chlorinated arylsulfonates, quinoxaline diand trithiocarbonates,chlorinated diarylsulfones and the like, fungicides, such as sulfur,dithiocarabamates and N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, to list but a few.

It is also desirable to combine the insecticidal products of thisinvention with a class of potentiators or synergists known in theinsecticidal art as knockdown agents. These substances are materialswhich may or may not be insecticidal themselves, but which when combinedwith other insecticides will shorten the time required, or reduce theamounts of the insecticide necessary to effect total immobilization(knockdown) or death of the insect to be controlled. Among the largenumber of synergists which may be employed are the organic thiocyanates,methylenedioxyphenyl compounds such as piperonyl butoxide,2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane, among others.

Yet another advantage of the invented compositions is that they mayreadily be formulated as solids or liquids using solid or liquidsolvents, vehicles, carriers or extenders. Suitable diluents are solidsor liquids usually of an inert nature. Illustrative solid diluentsinclude, among many others, sawdust, clay, flours, silicas, alkalineearth carbonates, oxides and phosphates, sulfur and the like. Suitablesolvents for liquid formulations include ketones, alcohols, aromatichydrocarbons, aliphatic hydrocarbons, and petroleum fraction ordistillates. Solutions in solvents such as these may be furtherdispersed in water by use of emulsifiers.

Whether dissolved or dispersed, suspended or emulsified in a liquid orformulated as a dust or powder or some other solid preparation, theinsecticides of this invention may advantageously contain one or moresubstances known or refered to variously as modifiers, wetting agents,surface active agents, dispersing agents, suspending agents, emulsifyingagents or conditioning agents, said materials being referred to hereingenerically as adjuvants. Thus, any substances which facilitatesformulation, handling and application of the insecticide of thisinvention may be profitably incorporated in the insecticidalcomposition. Frequently, such adjuvants enhance or potentiate insecticidal effectiveness. A satisfactory but not exhaustive list of thesesubstances appears among other places in Soap and Chemical Specialties,vol. 31; No. 7, pp. 50-61; No. 8, pp. 48-61; No. 9, pp. 52-67 and N0.10, PP. 3867 (1955). Another source of this information is BulletinE-607 of the Bureau of Entomology and Plant Quarantine of the UnitedStates Dept. of Agriculture.

The insecticidal compositions of this invention may be applied as a dustor a spray using among other things any of the above-mentionedexemplified formulations. The preferred method of application is a sprayincluding petroleum fractions or distillates as diluents, plus one ormore conditioning agents as formulation adjuvants. Ordinarily, a typicalspray will contain between about 0.001 percent and about ten percent byweight of the invented insecticide with the remaining material beingmade up largely of solvent with a small amount of adjuvants.

In order that the invention may be more fully understood, the followingexamples are given by way of illustrations, but the invention is notlimited thereto.

In the specification, examples, and claims, parts are by weight andtemperatures are in degrees centigrade unless otherwise indicated.

EXAMPLE 1 Preparation of dialkoxyoxophosphorane sulfenyl chlorides To asolution of 0.1 mole of trialkyl thiophosphate dissolved in 50milliliters of carbon tetrachloride was added dropwise a mixture of 13.5grams of sulfuryl chloride dissolved in 40 milliliters of carbontetrachloride. The temperature was held below 30 degrees centigradeduring the reaction. After 16 hours of agitation, the solution was readyfor use.

EXAMPLE 2 0,0-diethy1 (3 methylcarbamyloxy-Z-chloropropenyl)phosphorothiolate was prepared by treating a solution of 11.3 grams ofpropargyl N-methyl carbamate in 96 milliliters of carbon tetrachloridewith 0.1 mole of diethoxyphosphorane sulfenyl chloride in a solutionprepared as Example 1. The mixture was stirred for 20 hours in thepresence of ultraviolet light at a temperature of 76 degrees centigrade.The lower phase is stripped of solvent under vacuum to leave a residueof 29 grams of the desired product, a pale mahogany colored oil whichanalyzes at 9.08 percent phosphorus. The calculated percentage ofphosphorus in C11H17C1NO5PS is 9.08.

bamyloxy]-2-chloro-3,3 dimethyl propenyl) phosphorothiolate asrepresented by the formula:

o H; (OgHtO)z1 -SCH=C ClJ3-OCO NHCH:

is prepared.

Similarly, the reaction of diethoxyoxophosphorane sulfenyl chloride withl-(methylcarbamyloxy)-2-butyne results in the compound represented bythe formula:

In a similar manner, the corresponding bromine compounds are prepared,such as 0,0-diethyl (3-dimethylcarbamyloxy-Z bromo 3,3 dimethylpropenyl)phosphorothiolate by utilizing dialkoxyoxophosphorane sulfenyl bromidein the place of dialkoxyoxophosphorane sulfenyl chloride.

EXAMPLE 3 0,0-diethyl (3-[ethylmercapto carbonyloxy]-2-chloropropenyl)phosphorothiolate is prepared by treating a solution of 14.4 grams ofO-propargyl S-ethyl thiolcarbonate (prepared from ethyl mercaptan,propargyl alcohol, and triethylamine) in 85 milliliters of carbontetrachloride dropwise with a solution containing 0.1 mole of In asimilar manner, other solvents such as trichloroethylene,tetrachloroethane, and ethyl ethers are employed in place of carbontetrachloride.

The corresponding bromine compounds are prepared by utilizingdiethoxyoxophosphorane sulfenyl bromide in place ofdiethoxyoxophosphorane sulfenyl chloride.

Likewise, the reaction of sulfenyl chloride with 1,4-bis- (ethylmercaptocarbonyloxy) butyne-2 (prepared from the bis chloroformate)results in the preparation of a compound of the formula:

0,0-diethyl (3-ethoxycarbonyloxy-2-chloro propenyl) phosphorothiolate isprepared from a solution of 12.8 grams of ethyl propargyl carbonate(prepared from ethyl chloroformate and propargyl alcohol) in 95milliliters of carbon tetrachloride by treatment with 0.1 mole ofdiethoxyoxophosphorane sulfenyl chloride. After 10 hours of irradiationwith ultraviolet light, at a temperature of 78 degrees Centigrade, thesolution is stripped of solvent and washed with 100 milliliters ofhexane. The hexane insoluble was dried resulting in the recovery of 33.6grams of the desired compound, a straw colored oil analyzing as 9.3percent phosphorus. The theoretical calculated for CmHmClOgPS ispercent.

The corresponding -2-bromo compound is prepared by utilizingdiethoxyoxophosphorane sulfenyl bromide in place ofdiethoxyoxophosphorane sulfenyl chloride.

The analogous reaction of diethoxyphosphorane sulfenyl chloride with bis(ethoxycarbonyloxy) butyne-2- (prepared from the his chloroformate)results in the preparation of a compound as represented by the formula:

0,0-diethyl (2-chloro-3-[phenylmercaptocarbonyloxy]- propenyl)phosphorothiolate is prepared from a solution of 19.2 grams ofS-phenyl-O-propargyl thiolcarbonate in 85 milliliters of carbontetrachloride treated dropwise with 0.1 mole of diethoxyoxophosphoranesulfenyl chloride solution. After 10 hours of treatment with ultravioletlight at 40 degrees centigrade, the solution was stripped of solventunder reduced pressure, extracted with 100 milliliters of hexane and thehexane insoluble oil reduced to dryness in vacuo to afford 28.6 grams ofproduct, a pale yellow oil analyzing as 16.7 percent phosphorus. Thetheoretical calculated for C H ClO PS is 16.2 percent.

EXAMPLE 6 The following compounds as shown in Table I were tested forsystemic activity on aphids and leaf miners.

In these systemic tests, infested bean plants were treated with anaqueous suspension at a rate of 64 pounds per acre, which corresponds toactual row treatment of one pound per acre. The insect mortality isnoted after 24 hours, with results as follows:

See footnotes at end of table.

TABLE I-Continued Systemic Aotivlty Test, Leaf Miner Compound Black BeanControl at Aphids, Per- 126 p.p.m.

cent Killed i i (C:HaO)zP-SCH=CHCH:OC-N(CH:)I 100 I? o (amour-scum:o1-cHo-b i I (CEbOhP-S oH=oH-cH=0-b-' o o i i amour-53 011:0 c1-oHi0o-*o o l +=Eflective control; 0=No control. For purposes of comparison.

EXAMPLE 7 EXAMPLE 8 The following compounds, as shown in Table II below,were tested for housefly mortality by spraying aqueous dispersions ofthe compound at the concentrations shown,

In a similar manner to Example 7, the following comonto adulthousefl'ies (Musca domestica) pounds were tested for their activityagainst various forms of insect life by spraying insect infested plantswith aqueous suspensions at the concentrations shown.

TABLE II Percent Killed Compound 100 100 100 n i (C HaO)2PS-CH=O 11-01120 47-0 z II (CHaO):P-SCH=C O1CH2OC'0C (CH3): 100 100 30 0 ll(clH50)flP-'SCH=CC1OH2OC O(CH2)IOCH3 100 For purposes of comparison.

The mortality was observed after 24 hours.

The corresponding bromine compounds were similarly tested and possesssimilar activity.

The mortality is observed after 24 hours, with results as follows:

1 1 EXAMPLE 9 In a similar manner to Example 8, the following compoundswere sprayed in aqueous dispersions at the concentration as shown inparts per million, on mite infested 12 1,1-dimethylpropargylN,N-dimethylcarbamate,

H CH3 (I? (C2Hto)z1 s0H=oHc-oo-mom),

p.p.m. p.p.rn. p.p.m.

EXAMPLE l0 0,0-diethyl-(2 chloro 3[tetrahydrofurfuryloxycarbonyloxy1propenyl) phosphorothiolate isprepared from a solution of 184 grams of tetrahydrofurfuryl propargylcarbonate in 86 milliliters of carbon tetrachloride by dropvvisetreatment with 0.1 mole of diethoxyphosphorane sulfenyl chloride. Afterhours of exposure to ultraviolet light (during which time thetemperature rises to 45 degrees), the solution is reduced to dryness andthe residue washed with 100 milliliters of hexane. The hexane insolubleis reduced to dryness to give grams of product, a straw colored oil,analyzing as 8.0 percent phosphorus. The theoretical calculated for C HClO PS is 8.3.

EXAMPLE 11 0,0-dia1kyl phosphorodithioates (dialkyl phosphorodithioicacid) A mixture of 183 grams (0.41 mole) of phosphorus pentasulfide (P 8and 300 milliliters of toluene is stirred and brought to 80 degreescentigrade. The appropriate anhydrous alcohol (0.36 mole) is then addedover a 2-hour period. The mixture is then brought to full reflux for 2more hours, cooled and filtered. If the alcohol used has a boiling pointlower than that of the toluene, it may be removed by topping with an 18"Vigreaux column. The average titer is 2.62 millequivalents of acid permilliliter of solution.

EXAMPLE 12 0,0-diethy1 (3-dimethy1 carbamyloxypropenyl)phosphorodithioate is prepared by refluxing a solution of 12.7 grams(0.1 mole) of propargyl N,N-dimethylcarbamate and 0.1 mole of0,0-diethylphosphorodithioic acid (prepared as above) in a total of 140milliliters of toluene for 18 hours. Titration of the residual acidityindicates 98 percent reaction. The residue is dried and a vacuum appliedto eflect 28.5 grams of the compound, a pale oil. It analyzes as 10.4percent phosphorus compared with 9.4 percent phosphorus theoretical.

By reacting the diethyl phosphorodithioic acid with In a similar manner,reaction of diethyl phosphorodithioic acid with 1,4-bis(dimethylcarbamyloxy) butyue-Z results in the compound represented bythe formula:

0,0-diethyl 3-(isopropoxycarbonyloxy) propenyl phosphorodithioate isprepared as in Example 12 using 14.2 grams (0.1 mole) of isopropylpropargyl carbonate, 0.1 mole of 0,0-diethyl phosphorothioate, and ml.of toluene. The product, a pale oil, weighs 32 grams and analyzes as10.5 percent phosphorus and 20.2 percent sulfur compared with 10.5percent phosphorus and 19.5 percent sulfur theoretical.

By reacting the diethyl phosphorodithioic acid with (1,1-dimethylpropargyl) isopropyl carbonate the compound having the formula:

is prepared.

In a similar manner, the reaction of diethyl phosphorodithioic acid with1,4-bis (isopropoxycarbonyloxy) butyne-Z results in the compoundrepresented by the formula:

0,0-diethyl 3 (ethylmercaptocarbonyloxy) propenyl phosphorodithioate isprepared as in Example 12 using 14.4 grams (0.1 mole) of S-ethylO-propargyl thiolcarbonate, 0,0-diethyl phosphorodithioate (0.1 mole)and 75 milliliters of toluene. Titration of the residual acid indicates97 percent reaction. The product is a yellow oil analyzing as 9.3percent phosphorus compared to 9.11 percent theoretical.

Analysis Phosphorus (in percent) 113%: Clgggtflrig Acetylenle ReactantProduct :88; P P

Calcu- Found lated 15 .1 (CH30)2POSC1 CH CCHaOCONHCHa(OHi0)|POSCH=CCIOHzOilNHOH; 011.... 10.7 10.9 16 (CHsO)2POSC1 CHCCHaOCON(CH3)2 (CHaO)iPOSOH=CC1-CH,OCON(CH|)1 011...- 10.3 10.0

0 17 (CIH50)2POSO1 CHECGH OCOCHgCHzOCHa(CzHa0)aPOSCH=CCICHaOiEOCHaCHiOCH; 011..-. 8.6 8.8 18 (CH;0)|POSC1 CH-CCHQOCOOCHPLT (CHaO)zPOSCH=CC1CH:OCOOGlL-Lj 011.... 8.6 8.0

19 (CHaOhPOSCI CH C (1151100 OOCHzCHsOCHs(CHsO):POSCH=CC1CHaOCOOCHQCHaOCHs 011.... 9.3 9.8 20 (OHaOMPOSOI CHCCHaOCOSCoHs (CH)2POSCH=CCICHIOCOSCQHi 011.... 8.5 8.5 21 (C|H)1POSC1 CHCCHzOCHO (C:HtO):POSCH=CC1CH:OCHO 011.... 11.1 11.5

0 22 (CHsO)aPSSH CHEC-CHnOi'J-NWHD: (CHi0):PSSCH=CHCH:Oi N(CHa)z 011-...10.9 10.9

' 0 23 (C:H50)2PSSH CH C-CHzOii-NHGH; (CaHiO):PSSCH=CHCHiO( NHCHi011.... 10. 11 11.4 24 (GIHsOMPSSH CHECH2OOHO (C:H50):PSSCH=CH-CH:OCHO011.... 11.3 11.4

0 O 25 (CHIO)2PSSH CH CCH 0i 2-l l (CrHr0)zPSSGH=CH-CHai)O- i 011....8.8 8. 1

26 (CHIO)2PSSH The data presented in Example 6 illustrate both thesystemic activity and the leaf miner control of the compounds of thisinvention. The data is compared with related compounds of the prior artand clearly demonstrates the superiority of the compounds of theinvention.

Another illustration of the advantage of these compounds in terms ofpotency is shown in Example 7 where the ability toer-adicate housefiiesis shown to be far greater for the compounds of the invention ascompared to compounds of the related art.

The very broad spectrum of activity of the compounds of the presentinstance is illustrated in Example 8 which indicates insect toxicitywhich is in addition to that found in Examples 6 and 7.

The acaricidal activity of compounds of the invention are demonstratedin Example 9.

The data presented in the aforementioned group of examples readilyindicate the preferred embodiments of the invention. Thus, where a broadspectrum of insect species control is desired, the preferred embodimentis found in the group, where X is hydrogen and Y is a carbamatestructure. These structures are also especially advantageous wheresystemic activity and action on internal pests such as leaf miners isconcerned.

Where intensive acaricidal activity is desired, the preferred embodimentlies in the group of compounds where X is chloride and Y isthiolcarbonate as demonstrated in Example 9.

wherein:

R and R are alkyl of from 1 to about 6 carbon atoms;

Q is selected from the group consisting of oxygen and sulphur;

X is selected from the group consisting of chlorine, bromine andhydrogen;

B and b are selected from the group consisting of hydrogen and alkyl of1 to about 6 carbon atoms;

Y is selected from the group consisting of wherein:

Z and Z are selected from the group consisting of hydrogen and an alkylof 1 to about 6 carbon atoms;

Z is selected from the group consisting of alkyl of 1 to about 6 carbonatoms, unsubstituted aryl of from 6 to about 14 carbon atoms, andchloro-substituted aryl of 6 to about 14 carbon atoms;

Q is selected from the group consisting of oxygen and sulfur; and

R is selected from the group consisting of hydrogen, alkyl of from 1 to6 carbon atoms and wherein B, B' and Y are as described as above, said Xsubstituent being hydrogen only when Q is sulfur. 2. A compound inaccordance with claim 1 wherein the substituent Y is o z ll N wherein Zand Z are selected from the group consisting of hydrogen and alkyl offrom 1 to about 6 carbon atoms. 3. A compound in accordance with claim 1wherein the substituent Y is 4. A compound in accordance with claim 1wherein the substituent Y is 5. A compound of the formula:

and Z are selected from the group consisting of hydrogen and alkyl offrom 1 to about 6 carbon atoms.

References Cited UNITED STATES PATENTS 0 3,059,014 10/1962 Miller et a1260-978 FOREIGN PATENTS 3/1962 Great Britain. 10/1960 France.

25 CHARLES B. PARKER, Primary Examiner.

ANTON H. SUTTO, Assistant Examiner.

US. Cl. X.R.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 3,325 Dated March l, l969 Inventor) Sheldon B. Greenbaum It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

r- Column 3, lines 8-50, the formula should appear as fol lows:

II II (C H 0) P--SCH=CCl--CH 0C-0CH Column 3, line 70, the formulashould appear as fol lows:

8 CH 0C0-0C H II I 2 5 (C H O P -S-C=CHCH 0CO0C H Column 5, line h,delete "alkylne" and insert alkyne Column 5, line 63, delete"carabamates" and insert carbamates Column 6, line 19, delete "refered"and insert referred Column 6, line 23, delete "substances" and insertsubstance Column 8, line 30, the formula should appear as fol Iowa:

II 0 CH OC-OC H 0 u 2 2 5, (c H o) P-s-c=cc1-cH o-c-oc H :ggi UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3J6 1,325Dated March J969 PAGE Z Inventor-(s) Sheldon B. Greenbaum It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 8, Table I, the second for'mula under the title heading Com oundshould appear as fol lows:

n J n Column 8, Table I, the last formula under the ti tle heading Comound should appear as fol lows:

Column l3, Example 2h, under the title heading Acetxlenic Reactant theformula should read as fol lows:

CHEC-CH OCHO Columns l3 and HI, Example 25, under the title headingProduct the formula should read as fol lows (c H 0) PsscH=cH-cH 0c If 0UNITED STATES PATENT OFFICE 5 9 CERTIFICATE OF CORRECTION Patent No- ,35 Dated March '4, I969 Inventor) Sheldon B. Greenbaum PAGE 3 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1 line 69, delete b' and insert B' SIGNED AND SEALED mm: B.EOBUYIIER, JR. emu flewhm J find-salon or Patents Amazing 0mm

